Method for manufacturing multilayer ceramic capacitor

ABSTRACT

A method for manufacturing a multilayer ceramic capacitor includes: producing a plurality of dielectric green sheets; producing therefrom a plurality of internal electrode-printed green sheets; producing therefrom a plurality of individually cut unsintered laminates by stacking some of the plurality of dielectric green sheets, as cover layers, and the plurality of internal electrode-printed green sheets together; producing therefrom element body precursors by applying a ceramic paste to side faces of the unsintered laminates for forming side margins thereon, wherein an application thickness of the ceramic paste is adjusted in a manner such that a thickness of the side margins is greater than a thickness of the cover layers in the final product; producing therefrom element bodies by sintering; and forming external electrodes on at least one of principal faces and on both end faces of the element bodies.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/084,303, filed Mar. 29, 2016, which claims priority to JapanesePatent Application No. 2015-069463, filed Mar. 30, 2015, each disclosureof which is incorporated herein by reference in its entirety.

The applicant herein explicitly rescinds and retracts any priordisclaimers or disavowals made in any parent, child or relatedprosecution history with regard to any subject matter supported by thepresent application.

BACKGROUND Field of the Invention

The present invention relates to a multilayer ceramic capacitorexhibiting excellent thermal shock resistance.

Description of the Related Art

In recent years, the high demand for smaller electronic components tosupport higher-density electronic circuits used in mobile phones, tabletterminals, and other digital electronic devices is accelerating thedevelopment of smaller, larger-capacitance multilayer ceramic capacitors(MLCC) which constitute these circuits.

The capacitance of a multilayer ceramic capacitor is directlyproportional to the dielectric constant of the material constituting thedielectric layers that in turn constitute the capacitor, the number ofdielectric layers, and the effective internal electrode layer area orspecifically the area of the overlapping parts of the internal electrodelayers led out to the external electrodes alternately, and is inverselyproportional to the thickness of one dielectric layer. Accordingly,meeting the demand for smaller multilayer ceramic capacitors requiresincreasing the dielectric constant of the material, reducing thethickness of the dielectric layer, and increasing the number ofdielectric layers.

However, reducing the thickness of the dielectric layer causes thedielectric laminate to undergo shrinkage strain during the sinteringstep of MLCC manufacturing process, which leads to delamination at theinterface of the internal electrode and dielectric layer and cracking ofthe dielectric layer, thereby presenting a problem that the targetcharacteristics cannot be ensured. To solve such problem, PatentLiterature 1 discloses suppressing the shrinkage stress generating atthe center of the dielectric layer in the direction of lamination, byadjusting the material of the internal electrode in such a way that theso-called “continuity” value of the internal electrode becomes lowertoward the center of the dielectric layer in the direction oflamination.

Furthermore, Patent Literature 2, for the purpose of providing a highlyreliable laminated ceramic electronic component capable of solving thecrack failures in the dielectric laminate caused by thermal shocksapplied in the mounting step, etc., discloses defining the continuity as(X−Y)/X, wherein X represents the length of a cross section of theinternal electrode cut along its center in the long-side direction,while Y represents the total sum of gaps formed by the voids of theinternal electrode present within the cross section, and setting theaverage of the continuities of the internal electrodes near theuppermost internal electrode in the direction of lamination, and thelowermost internal electrode in the direction of lamination, of thedielectrics, in such a way that it is lower than the average of thecontinuities of the remaining internal electrodes.

Incidentally, while FIG. 6 shows a rough perspective view of arepresentative multilayer ceramic capacitor, generally the faces onwhich the internal electrode layers are led out to left and rightexternal electrodes 104 are called “end faces” 102 a, b, the top andbottom faces in the direction of lamination of internal electrode layersand dielectric layers are called “principal faces” 102 c, d, and theremaining pair of faces are called “side faces” 102e, f, in the case ofthe multilayer ceramic capacitor 100.

Furthermore, while the multilayer ceramic capacitor 100 has externalelectrodes on both of its end faces for connecting to a board, etc., asshown in FIG. 6, these external electrodes generally wrap around theother four faces in addition to the two end faces (so-called five-faceelectrodes) to allow for a board, etc., to be connected to any of thefaces.

Background Art Literatures

[Patent Literature 1] Japanese Patent Laid-open No. Hei 11-31633

[Patent Literature 2] Japanese Patent Laid-open No. 2006-332334

SUMMARY

The constitutions disclosed in Patent Literatures 1 and 2 have voidparts provided in the internal electrode layers, but presence of suchvoids reduces the effective area of internal electrode layers andthereby reduces the capacitance of the multilayer ceramic capacitor.

In addition, the multilayer ceramic capacitor has cover layers formed onit for the purpose of covering the top and bottom of the dielectriclaminate in the direction of lamination, and these cover layers arenormally formed using material similar to the material of the dielectriclayer. Accordingly, the capacitance of the capacitor can be increased byreducing the thickness of the cover layer and thereby increasing thenumber of internal electrode layers to be stacked.

However, reducing the thickness of the cover layer causes the thermalshock resistance of the multilayer ceramic capacitor to drop and makesit easy for cracks to generate in the cover layer, particularly wherethe external electrode is wrapped around the principal face, and itbecame clear that such a problem of cracks cannot be solved by theconstitutions proposed in Patent Literatures 1 and 2.

Accordingly, a primary object of the present invention is to provide alarge-capacitance multilayer ceramic capacitor exhibiting excellentthermal shock resistance while suppressing generation of crackssufficiently. In addition, a secondary object of the present inventionis to achieve high thermal shock resistance, and sufficiently suppressgeneration of cracks, in a large-capacitance multilayer ceramiccapacitor having extremely thin cover layers of 30 μm or less.

Any discussion of problems and solutions involved in the related art hasbeen included in this disclosure solely for the purposes of providing acontext for the present invention, and should not be taken as anadmission that any or all of the discussion were known at the time theinvention was made.

After studying in earnest to achieve the aforementioned objects, theinventors of the present invention found that, by limiting the faces onwhich the external electrode is formed to reduce the stress generatingas a result of thermal expansion of the external electrode, and also bymaintaining a specific relationship between the thickness of theexternal electrode and thickness of the cover layer, a large capacitancecould be achieved and at the same time the thermal shock resistance ofthe multilayer ceramic capacitor could be increased to sufficientlysuppress generation of cracks, and thereby completed the presentinvention.

In other words, the present invention is a multilayer ceramic capacitorhaving an element body of roughly rectangular solid shape which isconstituted by dielectric layers alternately stacked with internalelectrode layers having different polarities, with a pair of coverlayers formed on it to cover the top and bottom faces in the directionof lamination of the foregoing, and which has a pair of principal faces,a pair of end faces, and a pair of side faces, wherein externalelectrodes are formed on the pair of end faces and at least one of thepair of principal faces of the element body, and Tt representing thethickness of the external electrode and Tc representing the thickness ofthe cover layer satisfy the relationship of Tt≤Tc.

From the viewpoint of preventing solder leaching when mounting themultilayer ceramic capacitor, preferably the thickness of the externalelectrode, or Tt, is greater than 1 μm.

In addition, when the thickness of the cover layer, or Tc, is 10 μm ormore but 30 μm or less, such thinness of the cover layer allows for anincrease in the number of internal electrode layers to be stacked andconsequent increase in the capacitance of the multilayer ceramiccapacitor, as well as improvement of the moisture resistance reliabilityof the capacitor.

According to the present invention, a multilayer ceramic capacitor canbe provided which has large capacitance and also exhibits excellentthermal shock resistance while sufficiently suppressing generation ofcracks.

For purposes of summarizing aspects of the invention and the advantagesachieved over the related art, certain objects and advantages of theinvention are described in this disclosure. Of course, it is to beunderstood that not necessarily all such objects or advantages may beachieved in accordance with any particular embodiment of the invention.Thus, for example, those skilled in the art will recognize that theinvention may be embodied or carried out in a manner that achieves oroptimizes one advantage or group of advantages as taught herein withoutnecessarily achieving other objects or advantages as may be taught orsuggested herein.

Further aspects, features and advantages of this invention will becomeapparent from the detailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features of this invention will now be described withreference to the drawings of preferred embodiments which are intended toillustrate and not to limit the invention. The drawings are greatlysimplified for illustrative purposes and are not necessarily to scale.

FIG. 1 shows a rough perspective view of a multilayer ceramic capacitorconforming to the present invention.

FIG. 2 shows a schematic view of a cross section of the multilayerceramic capacitor 10 conforming to the present invention, cut inparallel with its side faces 12 e, f

FIG. 3 shows a schematic view of a cross section of the multilayerceramic capacitor 10, cut in such position that the internal electrodelayer 18 running in parallel with the principal faces 12 c, d isvisible.

FIG. 4A, FIG. 4B, and FIG. 4C show schematic views showing one exampleof how side margins are formed.

FIG. 5 shows a schematic view showing one example of how side marginsare formed.

FIG. 6 shows a rough perspective view of a representative multilayerceramic capacitor.

DESCRIPTION OF THE SYMBOLS

10 Multilayer ceramic capacitor

12 a, b End face

12 c, d Principal face

12 e, f Side face

14 External electrode

16 Element body

17 Dielectric layer

18 Internal electrode layer

20 Laminate

22 Cover layer

24 Side margin

30 Normal line of the bottom internal electrode layer

32 Position corresponding to the end of the internal electrode layer

34 Normal line of the cover layer

100 Multilayer ceramic capacitor

102 a, b End face

102 c, d Principal face

102 e, f Side face

104 External electrode

200 Internal electrode pattern

202 Bar-like laminate

204 Side margin

206 Laminate chip

300 Laminate chip

302 Group stage

304 a to d Block material

306 Squeegee

DETAILED DESCRIPTION OF EMBODIMENTS

The multilayer ceramic capacitor in an embodiment of the presentinvention is explained below. FIG. 1 is a rough perspective view of amultilayer ceramic capacitor 10 conforming to the present invention.Also under the present invention, the faces on which the internalelectrode layers are led out to left and right external electrodes 14are called “end faces” 12 a, b, the top and bottom faces in thedirection of lamination of the internal electrode layers and dielectriclayers are called “principal faces” 12 c, d, and the remaining pair offaces are called “side faces” 12 e, f, as under the prior art.

[Multilayer Ceramic Capacitor]

FIG. 2 shows a schematic view of a cross section of the multilayerceramic capacitor 10 conforming to the present invention, cut inparallel with its side faces 12 e, f. The multilayer ceramic capacitor10 is generally constituted by an element body 16 having standardizedchip dimensions and shape (such as rectangular solid of 1.0×0.5×0.5 mm),as well as a pair of external electrodes 14 primarily formed on both endface sides of the element body 16. The element body 16 has a laminate 20whose primary component is grain crystal of BaTiO₃, CaTiO₃, SrTiO₃,CaZrO₃, etc., and which is constituted by dielectric layers 17alternately stacked with internal electrode layers 18, as well as a pairof cover layers 22 formed as the uppermost and lowermost layers in thedirection of lamination to cover the top face and bottom face of thelaminate 20. Additionally, though not illustrated, there are sidemargins 24 that form the pair of side faces 12 e, f by covering thelaminate 20 (internal electrode layers 18 thereof) so it will not beexposed to the outside (refer to FIG. 3).

The laminate 20 is such that the thickness of the internal electrodelayer 18 and that of the dielectric layer 17 sandwiched by two internalelectrode layers 18 are set within specified ranges according to thestatic capacitance, required withstand voltage, and otherspecifications, and has a high-density multi-layer structure consistingof a total of around several hundred to a thousand layers.

The cover layers 22 and side margins 24 formed around the laminate 20protect the dielectric layers 17 and internal electrode layers 18against moisture, contaminants and other polluting substances from theoutside and prevent them from deteriorating over time.

Also, the internal electrode layers 18 are alternately led out to andelectrically connected at their edges with a pair of external electrodes14 that are present on both ends of the dielectric layers 17 in thelength direction and that each have a different polarity.

The thickness of the cover layer 22, or Tc, is not limited in any way,but under the present invention, it is preferably 30 μm or less, or morepreferably 10 μm or more but 30 μm or less, from the viewpoint ofincreasing the capacitance of the multilayer ceramic capacitor 10. WhenTc is 30 μm or less, the number of internal electrode layers 18 to bestacked can be increased by the reduced thickness of the cover layer 22,which allows the capacitance of the multilayer ceramic capacitor 10 tobe increased. Also, when Tc is 30 μm or less, the thermal shockresistance of the capacitor 10 tends to drop, but due to theconstitution of the present invention described later, the effect ofimproving the thermal shock resistance of the capacitor 10 becomespronounced. And, when Tc is 10 μm or more, the capacitor 10 alsoexhibits moisture resistance reliability.

Under the present invention, the thickness of the cover layer 22, or Tc,is obtained as follows. A cross section is cut off from the multilayerceramic capacitor 10 in parallel with the side faces 12 e, f and it isobserved with an optical microscope at a magnification of 200 times. Animage like the one shown in FIG. 2 is obtained, for example, and in thisimage, the maximum value of the length L (thickness), from the point ofintersection between a normal line 30 (there are multiple normal lines)of the internal electrode layer 18 at the top end or bottom end of thelaminate 20 and the interface of the internal electrode layer 18 at theapplicable end and the cover layer 22, to the point of intersectionbetween the cover layer 22 and its exterior and the normal line 30, isobtained. This is repeated for 10 multilayer ceramic capacitors 10, forexample, and the average of the 10 maximum values of L is used as thethickness of the cover layer 22, or Tc, under the present invention. Inembodiments, the greatest thickness L refers to a greatest thickness ofthe cover layer 22 constituting the principal face 12 d (or 12 c)wherein a thickness of the cover layer 22 varies due to ordinarymanufacturing variance, rather than intentional change in dimension.

Also under the present invention, a Tc of 30 μm or less, for example,means that the thickness Tc is 30 μm for each of the cover layers 22 atthe top and bottom of the laminate 20.

Under the present invention, preferably the cover layer 22 is formedthinly as described above, but this way the thermal shock resistance ofthe multilayer ceramic capacitor 10 may drop and cracks may generate inthe various steps involving heat, such as when mounting the capacitor10.

Under the present invention, (1) external electrodes 14 are formed onthe pair of end faces 12 a, b and at least one of the pair of principalfaces 12 c, d of the element body 16, and (2) Tt representing thethickness of the external electrode 14 and Tc representing the thicknessof the cover layer 22 satisfy the relationship of Tt≤Tc, in order toprevent such drop in thermal shock resistance.

In (1) above, since the external electrode 14 generally has a highercoefficient of thermal expansion than the dielectrics primarilyconstituting the element body 16, stress generates in the element body16 and this stress can cause cracking easily. With a conventionalmultilayer ceramic capacitor, the external electrodes wrap around notonly the two end faces, but also the remaining four faces, as explainedin the section of “Related Art”, and this leads to greater impact ofthermal expansion and easy generation of cracks.

Accordingly, under the present invention, the constitution in (1) aboveis adopted and external electrodes are substantially not formed on thepair of side faces 12 e, f, in order to reduce this impact of thermalexpansion (refer to FIG. 1).

Incidentally, “substantially not formed on the pair of side faces 12 e,f” includes not only where external electrodes 14 are not present at allon the entire side faces 12 e, f, but also where the external electrodes14 extend partially or slightly to the side faces. To be specific, whileFIG. 3 is a schematic cross sectional view of the multilayer ceramiccapacitor 10, cut in such position that the internal electrode layer 18running in parallel with the principal faces 12 c, d is visible, anexternal electrode 14 may be formed on the side face 12 f from the pointof intersection between the side face 12 f and end face 12 a, to aposition 32 corresponding to the end, on the end face 12 a side, of theinternal electrode layer 18 led out to the end face 12 b side, forexample. The same applies to the end face 12 b and side face 12 e on theopposite side. That is, no external electrodes are formed in a region Rof the pair of side faces 12 e, 12 f where the internal electrode layers18 having different polarities overlap as viewed in a thicknessdirection.

Also, under the present invention, external electrodes 14 are formed onat least one of the pair of principal faces 12 c, d, which means thatsubstantially no external electrode 14 may be formed on one principalface 12 c, for example. Here, “substantially no external electrode 14may be formed on one principal face 12 c” includes not only where anexternal electrode 14 is not present at all on the entire principal face12 c, but also where an external electrode 14 extends partially orslightly to the principal face 12 c from the point of intersectionbetween the principal face 12 c and end face 12 a, at maximum up to theposition corresponding to the end, on the end face 12 a side, of theinternal electrode layer 18 led out to the end face 12 b side, forexample (the end of the region R), as is the case with the side faces 12e, f The same applies to the end face 12 b on the opposite side.

Under the present invention, with respect to the principal faces 12 c,d, preferably external electrodes 14 are formed on only one of the pairof principal faces 12 c, d (i.e., substantially or completely noexternal electrodes 14 are formed on the other of the pair of principalfaces 12 c, d). This way, the absence of external electrodes on theother principal face allows for an increase in the number of internalelectrode layers 18 to be stacked, and consequently an increase in thecapacitance of the multilayer ceramic capacitor 10. Another reason isthat the impact of the external electrodes 14 of high coefficient ofthermal expansion decreases compared to when they are formed on bothprincipal faces. On the principal face where the external electrodes 14have been formed, the external electrodes 14 do not cover the entireprincipal face, but they are formed on the end face 12 a side and endface 12 b side separated with a certain distance. In addition, thethickness of the external electrode 14, or Tt, represents the overallthickness including the base electrode contacting the ceramics and theplating constituted by Cu, Ni, Sn, etc.

Then, regarding (2) above, or “Tt representing the thickness of theexternal electrode 14 and Tc representing the thickness of the coverlayer 22 satisfy the relationship of Tt≤Tc,” the thickness of theexternal electrode 14, or Tt, is obtained as follows under the presentinvention. A cross section is cut off from the multilayer ceramiccapacitor 10 in parallel with the side faces 12 e, f and it is observedwith an optical microscope at a magnification of 200 times. An imagelike the one shown in FIG. 2 is obtained, for example, and in thisimage, the maximum value of the length D (thickness), from the point ofintersection between a normal line 34 (there are multiple normal lines)on the principal face on the cover layer 22 and the interface of thecover layer 22 and external electrode 14, to the point of intersectionbetween the interface of the external electrode 14 and its exterior andthe normal line 34, is obtained. This is repeated for 10 multilayerceramic capacitors 10, for example, and the average of the 10 maximumvalues of D is used as the thickness of the external electrode 14, orTt, under the present invention. In embodiments, the greatest thicknessD refers to a greatest thickness of the external electrode 14 on theprincipal face 12 d (or 12 c) wherein a thickness of the externalelectrode 14 on the principal face 12 d (or 12 c) varies due to ordinarymanufacturing variance, rather than intentional change in dimension.

While the boundary of the principal face and end face is not clear inFIG. 2, in this case the principal face is considered to start from theend of the curved part of the end face.

Under the present invention, the Tt thus defined and the cover layerthickness Tc satisfies the condition of Tt≤Tc, or specifically thethickness of the external electrode 14 (where it overlaps with the coverlayer 22) is equal to or less than the thickness of the cover layer 22.By keeping the cover layer 22 at a thickness equal to or greater thanthe thickness of the external electrode 14 of high coefficient ofthermal expansion, as described above, the stress generated from thethermal expansion of the external electrode 14 caused by various thermalshocks in the mounting of the multilayer ceramic capacitor 10 and othersteps can be reduced and generation of cracks can be prevented.

While under the present invention the external electrodes 14 are formedon at least one of the pair of principal faces 12 c, d, as describedabove, if they are formed on both of these faces, then the condition ofTt≤Tc is satisfied by both external electrodes 14.

Then, from the viewpoint of preventing solder leaching when themultilayer ceramic capacitor 10 conforming to the present invention ismounted, preferably the thickness of the external electrode, or Tt, isgreater than 1 μm.

In addition, from the viewpoint of increasing the capacitance of themultilayer ceramic capacitor 10 conforming to the present invention,preferably the thickness of the dielectric layer 17 is kept to 0.8 μm orless. This is because, by reducing the thickness of the dielectric layer17, the capacitance increases and also the number of internal electrodelayers 18 to be stacked can be increased by the reduced thickness of thedielectric layer 17.

Also, while the thickness of the internal electrode layer 18 and that ofthe side margin 24 are not limited in any way with the multilayerceramic capacitor 10 conforming to the present invention, the thicknessof the internal electrode layer 18 is normally 0.26 to 1.00 μm, whilethe thickness of the side margin 24 is normally 4 to 50 μm.

[Manufacturing Method of Multilayer Ceramic Capacitor]

Next, the manufacturing method of the multilayer ceramic capacitorconforming to the present invention as described above is explained.

First, material powder for forming the dielectric layer is prepared. Forthe material powder, BaTiO₃, CaTiO₃, SrTiO₃, CaZrO₃ and various otherpowders that can be used to form ceramic sintered compact can be used.

These powders can be synthesized by causing various metal materials toreact together. Various synthesizing methods are known, such as thesolid phase method, sol-gel method, and hydrothermal method, amongothers. Under the present invention, any of these methods can beadopted.

To the obtained material powder, compounds that constitute secondaryconstituents can be added by specified amounts according to thepurposes. Secondary constituents include oxides of rare earths such asNd, Sm, Eu, Gd, Tb, Dy, Ho, and Er, as well as oxides of Mg, Mn, Ni, Co,Fe, Cr, Cu, Al, Mo, W, V, and Si.

The material powder obtained as above can be pulverized to adjust thegrain size, or pulverized and then classified to regulate the grainsize, as necessary, for example.

Then, binder such as polyvinyl butyral (PVB) resin, organic solvent suchas ethanol or toluene, and plasticizer such as dioctyl phthalate (DOP)are added to the material powder and the ingredients are wet-mixed. Theobtained slurry is applied on a base material in strips using thedie-coater method or doctor blade method, for example, after which theslurry is dried to obtain a dielectric green sheet of 1.2 μm or less inthickness. Then, on the surface of the obtained dielectric green sheet,a metal conductive paste containing organic binder is printed by meansof screen printing or gravure printing to arrange patterns of internalelectrode layers to be led out alternately to the pair of externalelectrodes each having a different polarity. For the aforementionedmetal, nickel is widely adopted from the viewpoint of cost.

Thereafter, the dielectric green sheet on which internal electrode layerpatterns have been printed is stamped out to specified sizes and thestamped-out dielectric green sheets are stacked together by a specifiednumber (such as 100 to 1,000 layers) so that when the base material isseparated, the internal electrode layers and dielectric layers arestaggered and also the edges of the internal electrode layers areexposed on both end faces of the dielectric layers in the lengthdirection and led out alternately to the pair of external electrodeseach having a different polarity. Cover sheets that will become thecover layers are pressure-welded on top and bottom of the stackeddielectric green sheets and the welded sheets/covers are cut tospecified chip dimensions (such as 1.0 mm×0.5 mm×0.5 mm in sizes aftersintering).

Here, while preferably the thickness of the cover layer 22, or Tc, is 30μm or less, as described above, Tc may be adjusted to a desired value byproperly selecting the conditions such as the amount of dielectric pasteto be applied on the base material when the cover sheet is formed, orthe printing type when dielectric paste is printed.

Also, for the method to form side margins, any of the various methodsthat are known can be adopted without any limitation at all; whencutting to the specified chip dimensions, for example, instead ofcutting exactly at the positions of the internal electrode layers, cut alittle wider so that parts of the dielectric layer not covered by theinternal electrode layer are also included because, this way, a sidemargin of desired thickness can be formed on both side faces of thelaminate to obtain an element body precursor that will become theelement body 16 after sintering.

Furthermore, a different method can be used to form side margins asfollows. To be specific, as shown in FIG. 4A, take multiple dielectricgreen sheets on which internal electrode patterns 200 have been printedin stripes at a specified interval (this interval corresponds to twicethe distance between the external electrode 14 and the edge of theinternal electrode layer 18 led out to the external electrode 14 on theopposite side of the aforementioned external electrode 14 in FIG. 2),and stack the dielectric green sheets so that the center of the stripeis superimposed with the interval part between the internal electrodepatterns 200.

Cut this along line C₁-C₁ so that the striped internal electrodepatterns 200 are cut across, to obtain a bar-like laminate 202 nothaving a pair of opposing side margins 204 as shown in FIG. 4B. Here,the cutting width (distance between the cross sections produced bycutting) corresponds to the size of the multilayer ceramic capacitor tobe manufactured, or specifically to the distance between the pair ofside faces 12 e, f of the element body 16.

Side margins 204 are formed on the side faces of the obtained bar-likelaminate 202 (normally side margins are formed using a material similarto that of the dielectric layers 17), which is then cut along line C₂-C₂into individual chip sizes (line C₂-C₂ passes through the center of aninternal electrode pattern 200 or center of the interval betweeninternal electrode patterns 200), to obtain individual laminate chips206 (FIG. 4C). On this chip 206, the internal electrodes are led outalternately on the cross sections produced by the aforementioned cuttingand this chip 206 represents an element body precursor that will becomethe element body 16 after sintering.

Also, a different method can be used to form side margins as follows. Tobe specific, as shown in FIG. 5, the laminate of dielectric green sheetsis cut exactly at the positions of the internal electrode layers orslightly inside, and the obtained laminate chips 300 (the internalelectrode layers are exposed on their side face) are arranged on a groupstage 302 so that their side face faces up. Then, on the group stage302, multiple block materials 304 a to 304 d that can slide in thedirections of the arrows as shown in the figure are caused to slide onthe group stage 302 in the directions of the arrows. This way, anaggregate of rectangular planar shape constituted by multiple laminatechips 300 adhering together is obtained.

Then, in this condition, a squeegee 306 is used to apply a ceramic paste(normally material similar to the one used to form the dielectric layers17) to form a ceramic paste layer of specified thickness on the top faceof the aggregate and then the paste is dried. This thickness can beadjusted by adjusting the difference between the height of the arrangedlaminate chips 300 and the height of the block materials 304.

Since the ceramic paste layer is formed over the entire surface of theaggregate of laminate chips 300, a roller may be run over the top faceof the aggregate under pressure or a blade may be pressed againstpositions corresponding to the boundaries of the laminate chips 300, todivide the ceramic paste layer to cover individual laminate chips 300.

This way, a side margin of specified thickness is formed on one sideface of the laminate chip 300, and by flipping the chip and repeatingthe same operation as described above, a side margin can be formed onthe other side face in a similar manner and an element body precursorthat will become the element body 16 after sintering can be obtained.

In addition, the corners of the element body precursor may be chamferedafter the cover layers and side margins have been formed, to shape theelement body precursor in such a way that the connection part of eachside of the element body precursor is curved. This way, chipping of thecorners of the element body precursor can be suppressed.

To achieve this shape, all that is needed is, for example, to put water,multiple element body precursors and polishing medium, into a sealedrotary pot made of polyethylene or other material, and rotate thissealed rotary pot to chamfer the corners of the element body precursors.

The element body precursors obtained as above, constituted by thelaminate of dielectric layers and internal electrode layers, coverlayers covering the top and bottom principal faces of the laminate, andside margins covering both side faces of the laminate, are put in an N₂ambience of 250 to 500° C. to remove the binder, and then sintered for10 minutes to 2 hours in a reducing ambience of 1100 to 1300° C., tosinter and densify each compound constituting the aforementioneddielectric green sheet. This way, the element body 16 of the multilayerceramic capacitor 10 conforming to the present invention is obtained.

Under the present invention, re-oxidizing treatment can also be given at600 to 1000° C.

Then, external electrodes 14 are formed on both end faces and at leastone principal face of the obtained element body 16. To form externalelectrodes at such specific positions, the method below may be adopted,for example.

The element bodies 16 are arranged so that their principal face or sideface contacts the bottom, and an external electrode paste constituted byCu or other metal grains, ethyl cellulose or other organic binder,dispersant, and solvent is applied to at least one principal face bymeans of printing, which external electrode paste is then dried to formexternal electrodes on the principal face. Thereafter, both end faces ofthe element body 16 are dip-coated with a similar paste, followed bydrying and baking. Thereafter, Ni/Sn plating film is formed.

The formation of external electrodes 14 on at least one principal facecan also be implemented by using, when forming the cover layers, coversheets whose surface has been pre-printed with external electrodepatterns.

Also, external electrodes 14 can be formed by means of sputtering ordeposition on the principal face and end face.

External electrodes 14 can be formed by various methods as describedabove and, when this forming is performed, the thickness of the externalelectrode 14, or Tt, can be adjusted to a desired value by adjusting theamount of external electrode paste to be applied during printing or byadjusting the sputtering amount or deposition amount in sputtering ordeposition.

This way, external electrodes 14 are formed on the pair of end faces andat least one of the pair of principal faces of the element body 16, andconsequently the multilayer ceramic capacitor 10 conforming to thepresent invention is obtained, where the thickness of the externalelectrode 14, or Tt, and the thickness of the cover layer 22, or Tc,satisfy a specified relationship.

EXAMPLES

The present invention is explained in greater detail below usingexamples. It should be noted, however, that the present invention is notlimited to these examples in any way.

[Manufacturing of Multilayer Ceramic Capacitor]

Dy and Mg were each added by 1.0 mol, and V and Mn were each added by0.5 mol, per 100 mol of barium titanate of 0.1 μm in average grain size,into which organic solvent whose primary constituent is alcohol,polyvinyl butyral resin, dispersant, and plasticizer were mixed anddispersed to produce a coating slurry. Then, this slurry was coated on abase material using a die-coater to produce a dielectric green sheet.The amount of slurry supplied to the die-coater was adjusted to controlthe thickness of the sheet.

Next, the aforementioned dielectric green sheet was screen-printed witha conductive paste prepared by mixing and dispersing Ni powder of 200 nmin average grain size, organic solvent whose primary constituent isalcohol, ethyl cellulose resin, dispersant, and plasticizer, to producea dielectric green sheet printed with internal electrodes. Theconcentration of solid matter in the conductive paste was adjusted bythe amount of paste solvent, to control the thickness of the internalelectrode.

Multiple layers of dielectric green sheets (for forming the coverlayers) and multiple layers of dielectric green sheets printed withinternal electrodes were stacked together and then pressure-bonded andcut to produce individual unsintered laminates. The number of dielectricgreen sheet layers was changed to change the thickness of the coverlayer.

The unsintered laminates were arranged so that their side margin face(side face) faced up, while Dy and Mg were each added by 1.0 mol, and Vand Mn were each added by 0.5 mol, per 100 mol of barium titanate of 0.1μm in average grain size, into which organic solvent whose primaryconstituent is alcohol, ethyl cellulose resin, dispersant, andplasticizer were mixed and dispersed to produce a ceramic paste. Then,this ceramic paste was applied to the top faces of the arrangedunsintered laminates and then dried, to form side margins. Theapplication thickness of the paste was adjusted to control the thicknessof the side margins. The opposing side margin face was also treated in asimilar manner, and an element body precursor was obtained as a result.

Water, multiple element body precursors, and polishing medium were putin a sealed rotary pot and this sealed rotary pot was rotated to chamferthe corners of the element body precursors.

The element body precursors thus obtained, each constituted by thelaminate of dielectric layers and internal electrode layers, coverlayers covering the top and bottom principal faces of the laminate, andside margins covering both side faces of the laminate, were put in an N₂ambience of 250 to 500° C. to remove the binder, and then sintered for10 minutes to 2 hours in a reducing ambience of 1100 to 1300° C.

The obtained element bodies were arranged so that their principal faceor side face contacted the bottom, and an external electrode pasteconstituted by Cu grains, ethyl cellulose, dispersant, and solvent wasapplied to one principal face by means of printing and then dried toform external electrodes on the principal face. Thereafter, both endfaces of the element body were dip-coated with a similar paste and thendried and baked. Thereafter, Ni/Sn plating film was formed.

Multilayer ceramic capacitors of the constitution shown below weremanufactured as described above:

Chip dimensions (L × W × H) 1.0 mm × 0.5 mm × 0.5 mm Thickness ofdielectric layer 0.7 μm Number of dielectric layers 315 layers Thicknessof internal electrode layer 0.7 μm Number of internal electrode layers315 layers Thickness of cover layer 8 to 30 μm Thickness of side margin35 μm Thickness of external electrode 1 to 36 μm (including plating)

The obtained multilayer ceramic capacitors in the examples andcomparative examples were each evaluated for various properties asdescribed below.

[Thermal Shock Resistance Test]

50 multilayer ceramic capacitors from each of the examples andcomparative examples were soaked for 1 second in a solder bath of 300°C. in temperature to check for presence or absence of cracks. “Passed”was indicated if none of the capacitors generated cracks.

[Moisture Resistance Test]

300 multilayer ceramic capacitors from each of the examples andcomparative examples were measured for the resistance of the capacitorin an environment of 85° C. in temperature and 85% in humidity after avoltage of 5 VDC was applied for 1,000 hours. “Passed” was indicated ifnone of the capacitors registered an insulation resistance of 10⁶Ω orless (moisture resistance abnormality).

[Mounting Test]

100 multilayer ceramic capacitors from each of the examples andcomparative examples were each mounted on a printed circuit board usingsolder and checked for contact. “Passed” was indicated if none of thecapacitors exhibited conductivity failure.

The results of the above evaluations are summarized in Table 1 below.

TABLE 1 Thickness of Thermal shock Moisture resistance Mounting testThickness of external resistance test test (Number of (Number of coverlayer Tc electrode Tt (Number of moisture resistance conductivity (μm)(μm) Tt/Tc cracks generated) abnormalities) failures) 8 9.8 (Comparative6/5 Failed (15) Failed (9) Failed (11) example) 6.4 (Example) 4/5 PassedFailed (6) Passed 1.6 (Example) 1/5 Passed Failed (4) Passed 1 (Example)1/8 Passed Failed (10) Passed 10 12 (Comparative 6/5 Failed (10) PassedFailed (9) example) 8 (Example) 4/5 Passed Passed Passed 2 (Example) 1/5Passed Passed Passed 1 (Example)  1/10 Passed Passed Passed 20 24(Comparative 6/5 Failed (7) Passed Failed (6) example) 16 (Example) 4/5Passed Passed Passed 4 (Example) 1/5 Passed Passed Passed 2 (Example) 1/10 Passed Passed Passed 1(Example)  1/20 Passed Passed Passed 30 36(Comparative 6/5 Failed (5) Passed Failed (3) example) 24 (Example) 4/5Passed Passed Passed 6 (Example) 1/5 Passed Passed Passed 3 (Example) 1/10 Passed Passed Passed 1(Example)  1/30 Passed Passed Passed

As is evident from Table 1, all of the comparative examples, where thethickness of the external electrode, or Tt, was greater than thethickness of cover layer, or Tc, failed the thermal shock resistancetest and mounting test; however, all of the examples where Tt was equalto or less than Tc passed the thermal shock resistance test and mountingtest.

In addition, the result of moisture resistance test was poor when Tc wasless than 10 μm, indicating that preferably Tc is 10 μm or more from theviewpoint of moisture resistance reliability.

In the present disclosure where conditions and/or structures are notspecified, a skilled artisan in the art can readily provide suchconditions and/or structures, in view of the present disclosure, as amatter of routine experimentation. Also, in the present disclosureincluding the examples described above, any ranges applied in someembodiments may include or exclude the lower and/or upper endpoints, andany values of variables indicated may refer to precise values orapproximate values and include equivalents, and may refer to average,median, representative, majority, etc. in some embodiments. Further, inthis disclosure, “a” may refer to a species or a genus includingmultiple species, and “the invention” or “the present invention” mayrefer to at least one of the embodiments or aspects explicitly,necessarily, or inherently disclosed herein. The terms “constituted by”and “having” refer independently to “typically or broadly comprising”,“comprising”, “consisting essentially of”, or “consisting of” in someembodiments. In this disclosure, any defined meanings do not necessarilyexclude ordinary and customary meanings in some embodiments.

It will be understood by those of skill in the art that numerous andvarious modifications can be made without departing from the spirit ofthe present invention. Therefore, it should be clearly understood thatthe forms of the present invention are illustrative only and are notintended to limit the scope of the present invention.

We/I claim:
 1. A method for manufacturing a multilayer ceramiccapacitor, comprising: (i) producing a plurality of dielectric greensheets constituted by barium titanate as a primary component; (ii)producing a plurality of internal electrode-printed green sheets byscreen-printing some of the plurality of dielectric green sheetsobtained in step (i) with a conductive paste; (iii) producing aplurality of individually cut unsintered laminates by stacking some ofthe plurality of dielectric green sheets, as cover layers, obtained instep (i) and the plurality of internal electrode-printed green sheetsobtained in step (ii) together to produce an unsintered laminate,followed by cutting the unsintered laminate; (iv) producing element bodyprecursors by applying a ceramic paste to side faces of the unsinteredlaminates obtained in step (iii) for forming side margins thereon,followed by drying the applied ceramic paste, wherein the ceramic pasteis constituted by barium titanate as a primary component, and anapplication thickness of the ceramic paste is adjusted in a manner suchthat a thickness of the side margins is greater than a thickness of thecover layers after step (v); (v) producing element bodies by removing abinder contained in the element body precursors obtained in step (iv),followed by sintering the binder-removed element body precursors in areducing ambience; and (vi) forming external electrodes on at least oneof principal faces and on both end faces of the element bodies obtainedin step (v).
 2. The method according to claim 1, wherein steps (iii) and(vi) are conducted in a manner such that Tt representing a thickness ofthe external electrodes and Tc representing a thickness of the coverlayers satisfy a relationship of Tt≤Tc.
 3. The method according to claim1, wherein the external electrodes in step (vi) contains Cu as anexternal electrode material.
 4. The method according to claim 1, whereinin step (vi), the external electrodes are formed by sputtering ordeposition on the principal face and the end faces.
 5. The methodaccording to claim 1, wherein step (iii) is conducted in a manner suchthat a thickness of the cover layers, or Tc, is 10 μm or more but 30 μmor less.